<i>In vitro</i> evaluation of Zn–10Mg–<i>x</i>HA composites with the core–shell structure

doi:10.1007/s11706-024-0699-3

Front. Mater. Sci.

2024, Vol. 18

Issue (3) : 240699 https://doi.org/10.1007/s11706-024-0699-3

In vitro evaluation of Zn–10Mg–xHA composites with the core–shell structure

Zeqin Cui^1,²(

), Qifeng Hu^1,², Jianzhong Wang³(

), Lei Zhou^1,², Xiaohu Hao^1,², Wenxian Wang^1,², Weiguo Li⁴, Weili Cheng¹, Cheng Chang⁵

¹. College of Materials Science and Engineering, Taiyuan University of Technology, Taiyuan 030024, China
². Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering, Taiyuan 030000, China
³. State Key Laboratory of Porous Metal Materials, Northwest Institute for Non-ferrous Metal Research, Xi’an 710016, China
⁴. Engineering Training Center, Taiyuan University of Technology, Taiyuan 030024, China
⁵. Guangdong Provincial Key Laboratory of Modern Surface Engineering Technology, National Engineering Laboratory of Modern Materials Surface Engineering Technology, Institute of New Materials, Guangdong Academy of Sciences, Guangzhou 510651, China

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Abstract

Zinc-based composites represent promising materials for orthopedic implants owing to their adjustable degradation rates and excellent biocompatibility. In this study, a series of Zn–10Mg–xHA (x = 0–5 wt.%) composites with the core–shell structure were prepared through spark plasma sintering, and their microstructural, mechanical, and in vitro properties were systematically evaluated. Results showed that the doped hydroxyapatite (HA) is concentrated at the outer edge of the MgZn₂ shell layer. The compression strength of the Zn‒10Mg‒HA composite gradually decreased with the increase of the HA content, while its corrosion rate decreased initially and then increased. The corrosion resistance of the composite with the addition of 1 wt.% HA was improved compared to that of Zn–10Mg–0HA. However, the further increase of the HA content beyond 1 wt.% resulted in a faster degradation of the composite. Moreover, the Zn–10Mg–1HA composite significantly enhanced the activity of MC3T3-E1 osteoblasts. Based on such findings, it is revealed that the composite containing 1 wt.% HA exhibits superior overall properties and is anticipated to serve as a promising candidate for bone implant materials.

Keywords zinc-based composite hydroxyapatite mechanical property in vitro degradation behavior biocompatibility

Corresponding Author(s): Zeqin Cui,Jianzhong Wang

Issue Date: 10 September 2024

Cite this article:

Zeqin Cui,Qifeng Hu,Jianzhong Wang, et al. In vitro evaluation of Zn–10Mg–xHA composites with the core–shell structure[J]. Front. Mater. Sci., 2024, 18(3): 240699.

URL:

https://academic.hep.com.cn/foms/EN/10.1007/s11706-024-0699-3
https://academic.hep.com.cn/foms/EN/Y2024/V18/I3/240699

Fig.1 Sample preparation: (a) temperature?time and pressure?time curves for SPS; (b) photographs of sintered samples.

Fig.2 Schematic illustration of a dynamic simulation device.

Tab.1 Theoretical, actual, and relative densities of tested samples

Fig.3 Microstructures and elemental distributions of samples: (a) morphologies of ZM?0HA, ZM?1HA, ZM?3HA, and ZM?5HA; (b) element distributions of ZM?0HA and ZM?3HA.

Tab.2 Elemental scanning analysis results of Zn and Mg for the core?shell structure

Fig.4 Microstructures and compositional analyses: (a) backscattering topography of the ZM–1HA composite; (b) energy spectrum analysis of the core–shell structure in the amplified region of Panel (a); (c) scanning results of the white straight line in the shell region of Panel (b); (d) XRD patterns of ZM?0HA, ZM?1HA, ZM?3HA, and ZM?5HA.

Fig.5 Mechanical properties of ZM?0HA, ZM?1HA, ZM?3HA, and ZM?5HA samples: (a) elastic moduli; (b) microhardness values; (c) compression properties; (d)(e)(f) load?displacement curves for matrix, shell, and core.

Fig.6 Fracture images of samples: (a) ZM?0HA; (b) ZM?1HA; (c) ZM?3HA; (d) ZM?5HA.

Fig.7 Electrochemical and dynamic degradation behaviors of ZM?0HA, ZM?1HA, ZM?3HA, and ZM?5HA samples: (a) polarization curves; (b) Nyquist plots; (c) average corrosion rates under different durations; (d) average corrosion rates after static and dynamic immersions for 7 d.

Tab.3 Corrosion properties of samples derived from the electrochemical test

Fig.8 Morphology observation and microstructures of samples after dynamic immersion: (a) surface morphologies of samples; (b) surface microstructures of samples after 30 d of immersion for ZM?0HA (b1) and ZM?1HA (b2); (c) microstructures of corrosion products on sample surfaces with corresponding EDS scans of ZM?0HA (c1)(c2) and ZM?1HA (c3)(c4); (d) XRD pattern of the degradation product.

Fig.9 Corrosion morphologies of ZM?0HA, ZM?1HA, ZM?3HA, and ZM?5HA samples after immersion for 7 and 30 d.

Fig.10 The 7-d immersion test results of ZM?0HA, ZM?1HA, ZM?3HA, and ZM?5HA samples: (a) variations of the pH values with the immersion time; (b) a schematic diagram of the hydrogen collection; (c) variations of the hydrogen evolution volumes with the immersion time; (d) variations of the corrosion rates with the immersion time.

Fig.11 Schematic diagrams of the corrosion degradation mechanism for composites: (a) galvanic corrosion; (b) exchange of HA ions.

Fig.12 Live/dead fluorescent images of osteoblasts after culturing for 1, 3, and 5 d on surfaces of ZM?0HA, ZM?1HA, ZM?3HA, and ZM?5HA samples.

Fig.13 MTT results of osteoblasts after culturing for 1, 3, and 5 d on surfaces of ZM?0HA, ZM?1HA, ZM?3HA, and ZM?5HA samples (**p < 0.01).

1	F Witte . The history of biodegradable magnesium implants: a review.Acta Biomaterialia, 2010, 6(5): 1680–1692 https://doi.org/10.1016/j.actbio.2010.02.028
2	N, Li Y F Zheng . Novel magnesium alloys developed for biomedical application: a review.Journal of Materials Science and Technology, 2013, 29(6): 489–502 https://doi.org/10.1016/j.jmst.2013.02.005
3	H T, Yang B, Jia Z C, Zhang et al.. Alloying design of biodegradable zinc as promising bone implants for load-bearing applications.Nature Communications, 2020, 11(1): 401 https://doi.org/10.1038/s41467-019-14153-7
4	G K, Levy J, Goldman E Aghion . The prospects of zinc as a structural material for biodegradable implants — a review paper.Metals, 2017, 7(10): 402 https://doi.org/10.3390/met7100402
5	S X, Zhang X N, Zhang C L, Zhao et al.. Research on an Mg–Zn alloy as a degradable biomaterial.Acta Biomaterialia, 2010, 6(2): 626–640 https://doi.org/10.1016/j.actbio.2009.06.028
6	M S, Song R C, Zeng Y F, Ding et al.. Recent advances in biodegradation controls over Mg alloys for bone fracture management: a review.Journal of Materials Science and Technology, 2019, 35(4): 535–544 https://doi.org/10.1016/j.jmst.2018.10.008
7	J, Kubásek D, Vojtěch I, Pospíšilová et al.. Microstructure and mechanical properties of the micrograined hypoeutectic Zn–Mg alloy.International Journal of Minerals Metallurgy and Materials, 2016, 23(10): 1167–1176 https://doi.org/10.1007/s12613-016-1336-7
8	C, Xiao L Q, Wang Y P, Ren et al.. Indirectly extruded biodegradable Zn–0.05wt%Mg alloy with improved strength and ductility: in vitro and in vivo studies.Journal of Materials Science and Technology, 2018, 34(9): 1618–1627 https://doi.org/10.1016/j.jmst.2018.01.006
9	S R, Dutta D, Passi P, Singh et al.. Ceramic and non-ceramic hydroxyapatite as a bone graft material: a brief review.Irish Journal of Medical Science, 2015, 184(1): 101–106 https://doi.org/10.1007/s11845-014-1199-8
10	R Z LeGeros . Calcium phosphate-based osteoinductive materials.Chemical Reviews, 2008, 108(11): 4742–4753 https://doi.org/10.1021/cr800427g
11	A K, Nayak M, Maity H, Barik et al.. Bioceramic materials in bone-implantable drug delivery systems: a review.Journal of Drug Delivery Science and Technology, 2024, 95: 105524 https://doi.org/10.1016/j.jddst.2024.105524
12	X H, Yu X Y, Tang S V, Gohil et al.. Biomaterials for bone regenerative engineering.Advanced Healthcare Materials, 2015, 4(9): 1268–1285 https://doi.org/10.1002/adhm.201400760
13	R, Sergi D, Bellucci R T Jr, Candidato et al.. Bioactive Zn-doped hydroxyapatite coatings and their antibacterial efficacy against Escherichia coli and Staphylococcus aureus.Surface and Coatings Technology, 2018, 352: 84–91 https://doi.org/10.1016/j.surfcoat.2018.08.017
14	J, Pinc E, Miklášová F, Průša et al.. Influence of processing on the microstructure and the mechanical properties of Zn/HA8 wt.% biodegradable composite. Manufacturing Technology, 2019, 19(5): 836–841 https://doi.org/10.21062/ujep/381.2019/a/1213-2489/MT/19/5/836
15	H T, Yang X H, Qu W J, Lin et al.. In vitro and in vivo studies on zinc‒hydroxyapatite composites as novel biodegradable metal matrix composite for orthopedic applications.Acta Biomaterialia, 2018, 71: 200–214 https://doi.org/10.1016/j.actbio.2018.03.007
16	Z, Zhen T F, Xi Y F Zheng . A review on in vitro corrosion performance test of biodegradable metallic materials.Transactions of Nonferrous Metals Society of China, 2013, 23(8): 2283–2293 https://doi.org/10.1016/S1003-6326(13)62730-2
17	A, Oyane H M, Kim T, Furuya et al.. Preparation and assessment of revised simulated body fluids.Journal of Biomedical Materials Research Part A, 2003, 65A(2): 188–195 https://doi.org/10.1002/jbm.a.10482
18	C H, Cai R B, Song L X, Wang et al.. Effect of anodic T phase on surface micro-galvanic corrosion of biodegradable Mg–Zn–Zr–Nd alloys.Applied Surface Science, 2018, 462: 243–254 https://doi.org/10.1016/j.apsusc.2018.08.107
19	Y, Zhao Y H, Sun W W, Lan et al.. Self-assembled nanosheets on NiTi alloy facilitate endothelial cell function and manipulate macrophage immune response.Journal of Materials Science and Technology, 2021, 78: 110–120 https://doi.org/10.1016/j.jmst.2020.10.054
20	X F, Gu L M, Zhang M J, Yang et al.. Fabrication by SPS and thermophysical properties of high volume fraction SiCp/Al matrix composites.Key Engineering Materials, 2006, 313: 171–176 https://doi.org/10.4028/www.scientific.net/KEM.313.171
21	S, Jaiswal R M, Kumar P, Gupta et al.. Mechanical, corrosion and biocompatibility behaviour of Mg–3Zn–HA biodegradable composites for orthopaedic fixture accessories.Journal of the Mechanical Behavior of Biomedical Materials, 2018, 78: 442–454 https://doi.org/10.1016/j.jmbbm.2017.11.030
22	K, Rezwan Q Z, Chen J J, Blaker et al.. Biodegradable and bioactive porous polymer/inorganic composite scaffolds for bone tissue engineering.Biomaterials, 2006, 27(18): 3413–3431 https://doi.org/10.1016/j.biomaterials.2006.01.039
23	Z Y, Zhang D, Wang L X, Liang et al.. Corrosion resistance of Ca–P coating induced by layer-by-layer assembled polyvinylpyrrolidone/DNA multilayer on magnesium AZ31 alloy.Frontiers of Materials Science, 2021, 15(3): 391–405 https://doi.org/10.1007/s11706-021-0560-x
24	R H, Yao Y Y, Zhao S Y, Han et al.. Microstructure, mechanical properties, in vitro degradation behavior and in vivo osteogenic activities of Zn–1Mg–β-TCP composites for bone defect repair.Materials & Design, 2023, 225: 111494 https://doi.org/10.1016/j.matdes.2022.111494
25	H R, Zheng M F, Chen Z, Li et al.. Effects of MgO modified HA nanoparticles on the microstructure and properties of Mg–Zn–Zr/m-HA composites.Acta Metallurgica Sinica, 2017, 53(10): 1364–1376 (in Chinese) https://doi.org/10.11900/0412.1961.2017.00249
26	J, Venezuela M S Dargusch . The influence of alloying and fabrication techniques on the mechanical properties, biodegradability and biocompatibility of zinc: a comprehensive review.Acta Biomaterialia, 2019, 87: 1–40 https://doi.org/10.1016/j.actbio.2019.01.035
27	Y H, Lao W W, Zhang X F, Xu et al.. Dynamic degradation behavior of AZ31 magnesium alloy in artificial plasma.Rare Metal Materials and Engineering, 2014, 43(5): 1242–1245
28	J, Kubásek D, Vojtěch E, Jablonská et al.. Structure, mechanical characteristics and in vitro degradation, cytotoxicity, genotoxicity and mutagenicity of novel biodegradable Zn–Mg alloys.Materials Science and Engineering C, 2016, 58: 24–35 https://doi.org/10.1016/j.msec.2015.08.015
29	J W, Lee B R, Park S Y, Oh et al.. Mechanistic study on the cut-edge corrosion behaviors of Zn–Al–Mg alloy coated steel sheets in chloride containing environments.Corrosion Science, 2019, 160: 108170 https://doi.org/10.1016/j.corsci.2019.108170
30	H, Kabir K, Munir C, Wen et al.. Recent research and progress of biodegradable zinc alloys and composites for biomedical applications: biomechanical and biocorrosion perspectives.Bioactive Materials, 2021, 6(3): 836–879 https://doi.org/10.1016/j.bioactmat.2020.09.013
31	S, Thomas N, Birbilis M S, Venkatraman et al.. Corrosion of zinc as a function of pH.Corrosion, 2012, 68(1): 015009 https://doi.org/10.5006/1.3676630
32	L, Zhang Z Y, He Y Q, Zhang et al.. Enhanced in vitro bioactivity of porous NiTi–HA composites with interconnected pore characteristics prepared by spark plasma sintering.Materials & Design, 2016, 101: 170–180 https://doi.org/10.1016/j.matdes.2016.03.128
33	J, Ma N, Zhao D H Zhu . Bioabsorbable zinc ion induced biphasic cellular responses in vascular smooth muscle cells.Scientific Reports, 2016, 6(1): 26661 https://doi.org/10.1038/srep26661
34	Z H, Zhang D B, Liu Z Y, Chen et al.. Fabrication, in vitro and in vivo properties of β-TCP/Zn composites.Journal of Alloys and Compounds, 2022, 913: 165223 https://doi.org/10.1016/j.jallcom.2022.165223

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